EP0803513B1 - Poröse feine teilchen und kosmetika - Google Patents

Poröse feine teilchen und kosmetika Download PDF

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Publication number
EP0803513B1
EP0803513B1 EP95912468A EP95912468A EP0803513B1 EP 0803513 B1 EP0803513 B1 EP 0803513B1 EP 95912468 A EP95912468 A EP 95912468A EP 95912468 A EP95912468 A EP 95912468A EP 0803513 B1 EP0803513 B1 EP 0803513B1
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Prior art keywords
particulate
deodorant
chitosan
porous particulate
polysiloxane
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EP95912468A
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French (fr)
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EP0803513A4 (de
EP0803513A1 (de
Inventor
Yoshihiro Wakayama Laboratory HASEBE
Michitaka Wakayama Laboratory SAWADA
Makoto Kao Corporation FURUKAWA
Takako Wakayama Laboratory NAKAYAMA
Kenji Kodama
Yasushi Wakayama Laboratory ITO
Genichi Wakayama Laboratory NAKAMURA
Yasuhisa Wakayama Laboratory FUKUMOTO
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Kao Corp
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Kao Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0279—Porous; Hollow
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/736—Chitin; Chitosan; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91—Graft copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00

Definitions

  • the present invention relates to a porous particulate which is useful in skin cosmetics (antiperspirants, deodorants, packs and humectants), hair care products, drugs, fiber treatments, paper coatings, cement additives, covering materials, bactericides/bacteriostats and agricultural chemicals.
  • the anionic/cationic amphoteric particulate derived through emulsification, suspension or the like is generally obtained by copolymerization of a monomer having an amino group and a monomer having an acidic group, or first forming an anionic or a cationic particulate and subsequently conducting a modification reaction to thereby convert a part of the reactive groups to cationic or anionic groups, or effecting compounding to thereby render cationic and anionic substances copresent.
  • processes for producing particulates with the use of natural raw materials include those in which chitosan having a primary amino group as a base is dissolved in an acid and the resultant solution is dropped into an alkaline coagulation fluid and those in which chitosan solutions or dispersions are mechanically treated.
  • all the obtained particulates are cationic, and only particles with a diametrical size of tens to hundreds of micrometers or more can be obtained thereby.
  • a granular complex of chitosan and an organic acid polymer is synthesized by a technique in which an organic acid having a reactive vinyl group is (co)polymerized in the presence of chitosan in an aqueous solution among various known techniques for producing amphoteric particles from basic polysaccharides as bases (see Kobunshi Ronbunshu (Reports of Polymer Science), Vol. 37, No. 3, 185 (1980)).
  • the chitosan particulate produced by the above technique has a broad particle size distribution and only nonspherical particles containing particles with a size of 50 ⁇ m or greater can be obtained. Furthermore the porosity thereof is low.
  • Body smells such as axillary, foot and sweat smells are unpleasant and serious distress to those having such smells.
  • the components of body smells are metabolites produced by the action of resident bacterial flora of the skin upon smell-causing sweat, egesta, putrefied matter and the like.
  • the secreted sweat per se does not cause strong smell, it generates lower carboxylic acids and volatile matter, which cause offensive smells, by the action of the resident bacterial flora of the skin.
  • the foul-smelling matter may be various and, for example, composed of a lower carboxylic acid such as acetic, butyric, propionic or isovaleric acid or a steroid.
  • Examples of the techniques for inhibiting the above body smells include a method (1) in which use is made of a metallic oxide such as zinc oxide, magnesium oxide, titanium oxide or alumina, a method (2) in which the physical adsorption of a porous substance such as active carbon is utilized, a method (3) in which use is made of an antibacterial drug capable of inhibiting the proliferation of the resident bacterial flora of the skin (for example, triclosan, isopropylmethylphenol, benzalkonium chloride, chlorhexidine, chlorhexidine gluconate or halocarban), a method (4) in which use is made of a strongly astringent drug (for example, zinc p-phenolsulfonate, citric acid, aluminum salt or zirconium salt), and masking by perfumes (5).
  • a metallic oxide such as zinc oxide, magnesium oxide, titanium oxide or alumina
  • a method (2) in which the physical adsorption of a porous substance such as active carbon is utilized
  • an antibacterial drug capable of
  • the physical deodorization using active carbon or the like has drawbacks not only in that the capacity of adsorbing lower fatty acids is not satisfactory but also in the comfort in the use thereof and the persistence of the effect thereof.
  • the sensory deodorization such as masking by the use of a perfume changes the quality of smelling substances by means of the perfume, its method effect is limited because smelling substances are still left.
  • the method using a metallic oxide such as zinc oxide, magnesium oxide, titanium oxide or alumina is not fully satisfactory because, although various measures for increasing the surface area of the metallic oxide have been taken to cope with the reaction of the metallic oxide with acids only on the surface of the metallic oxide, gelation is caused by the reaction of the metallic oxide with acids as foul-smelling substances despite the increase of the surface area of the metallic oxide, so that the capacity is poor for capturing acids generated with the passage of time.
  • Japanese Patent Laid-Open No. 290808/1988 discloses a deodorant and bactericidal cosmetic, whose deodorant effect is, however, little if any.
  • Japanese Patent Laid-Open Nos. 190110/1987 and 235906 /1992 describe that the addition thereof to cosmetics such as foundations and eye shadows improves the comfort in the use of the cosmetics and the make-up, stability and moldability of the cosmetics.
  • the deodorant When applied to the skin by, for example, coating, the deodorant forms some film on the skin, thereby playing a role to help to prevent the scattering of active ingredients by means of the film formed on the skin.
  • Paraffin wax, vaseline and other compounds that are solid or semisolid at room temperature are being employed as film formers. Although their film-forming effects are so high as to ensure a prolonged holding of active ingredients, they prevent the cutaneous respiration and the evapotranspiration of steam. Thus, especially at high temperatures, for example, in summer, they are detrimental to the skin.
  • silicone oil has recently come to be used as an oil for applying deodorants to the skin.
  • the major reason therefor is an improvement in the touch such as an increased slidability attributed to the extremely low intermolecular force of the silicone oil.
  • the silicone oil would be free from the above problem of preventing the cutaneous respiration and the evapotranspiration of steam as caused by, for example, waxes because of its high permeabilities to gases and steam.
  • the silicone oil has such a low surface tension that it is likely to diffuse on the skin with the result that no persistent film can be formed for the active ingredients.
  • the use of siloxanes is disclosed in JP-A 5-255056.
  • Polysiloxanes having long-chain alkyl groups, as bases capable of forming films on the skin are applied, in skin care preparations. These utilize the crystallinity of the alkyl groups, and a mixture of a plurality of polysiloxanes functions while a polysiloxane having alkyl groups at its both ends alone functions to inhibit the evapotranspiration of moisture from dry skin, these polysiloxanes are not only do they become oily and sticky to the touch near the body temperature because of their low melting points but also the durability of each of the films at high temperatures becomes poor.
  • the polysiloxane for use in the present invention effectively utilizes the high steam permeability of the silicone contrary to the above functions. And the polysiloxane does not prevent the evapotranspiration of moisture while it has the property of persistently holding the active ingredients on the skin. So, it can be advantageously used especially in a period of profuse sweating in summer.
  • Patent abstracts of Japan, Vol. 15, No. 345, JP 03/134038 describes a particulate material which is prepared by copolymerizing chitosan, an organic acid capable of dissolving chitosan and having a reactive vinyl group, and at least one monomer copolymerizable with the acid.
  • the particulate material has a wide range of particle diameters.
  • Patent abstracts of Japan, Vol. 18, No. 32, JP 05/262616 describes a cosmetic containing a long-chain hydrocarbon group-modified silicon compound which may be obtained by a hydrosilylation reaction between polymethylhydrogensiloxane and an ⁇ -olefin or a fatty acid allyl ester. This compound has an excellent compatibility with a hydrocarbon oil used as a raw material of a cosmetic.
  • Patent abstracts of Japan, Vol. 10, No. 269, JP 61/095014 describes a water-absorbing material containing a polysaccharide which is copolymerized with one or more monomers (meth)acrylic esters. This may be used as a water-absorbing material useful as a sanitary napkin.
  • JP 63/290808 describes an antibacterial deodorant cosmetic containing equal or more than 1 wt. % of a water-soluble acid salt of chitosan.
  • Another object of the present invention is to provide a cosmetic such as a deodorant which has a high deodorant effect and is excellent in immediacy and persistence.
  • the task of the present invention is to provide a deodorant excellent in the persistence of deodorant effect which forms a film capable of persistently holding active ingredients on the skin without preventing the cutaneous respiration and the evapotranspiration of steam when applied to the skin. thus being able to prevent the scattering and flow down of active ingredients.
  • amphoteric porous particulate based on a basic polysaccharide as a natural material which has both anionic and cationic properties and which contains basic and acid group capable of reacting with strong acids and bases in polar or nonpolar solvents in amounts per particle strikingly greater than the case of the conventional particulates. Further, they have that the use of this amphoteric porous particulate leads to the exertion of deodorant performance of having extremely high acid capturing properties to thereby be free from the lowering of acidic substance capturing capability with the lapse of time.
  • the present invention has been completed on the basis of these findings.
  • the present invention mainly provides a porous particulate having a deodorant effect, a process for producing the same, a cosmetic composition containing the same, a cosmetic composition containing a chitosan particulate as a deodorant and a cosmetic containing polysiloxane as an oil, especially a deodorant composition.
  • the present invention provides an amphoteric porous particulate comprising a polymer of a basic polysaccharide and an organic acid containing a reactive vinyl group or a salt thereof and having an average particle size of 50 ⁇ m or less. It is preferred that the porous particulate be composed of spherical fine particles, that the specific surface area of the porous particulate be in the range of 10 to 300 m 2 /g, that the basic polysaccharide be chitosan, and that the organic acid containing a reactive vinyl group or salt thereof be methacrylic acid or a salt thereof.
  • This particulate may be produced by emulsifying or suspending an aqueous solution containing a basic polysaccharide and an organic acid having a reactive vinyl group in a hydrophobic solvent and thereafter effecting polymerization thereof. It is preferred that, after the polymerization, a polymerization reaction mixture be dropped into or added at once to an organic solvent containing a base to thereby precipitate a porous particulate.
  • the organic acid may be used in a molar amount of 0.1 to 500 times the number of moles of monosaccharide units composing the basic polysaccharide.
  • the present invention provides a cosmetic composition containing the above amphoteric porous particulate preferably in an amount of 0.1 to 70% by weight and being useful as a deodorant.
  • the cosmetic composition may contain ingredients conventionally employed in cosmetic recipes.
  • it may contain an oil.
  • the present invention contains an amphoteric porous particulate of spherical fine particles, which comprises a polymer of a basic polysaccharide and an organic acid containing a reactive vinyl group and having an average particle size of 50 ⁇ m or less.
  • the present invention provides a chitosan particulate having an average particle size of 0.01 to 50 ⁇ m as a deodorant, a cosmetic composition, for example, a deodorant containing the same, and a method of deodorization using the same.
  • the chitosan particulate have a specific surface area of 10 to 300 m 2 /g, that the chitosan particulate have an available amino group content of 1.0 ⁇ 10 -7 to 1.0 ⁇ 10 -2 mol/g, and that the chitosan particulate be composed of spherical fine particles.
  • the present invention provides a polysiloxane having alkyl groups of at least 16 carbon atoms on the average and a melting point of 20°C or above as the oil component for a cosmetic, especially a deodorant.
  • the present invention provides a composition containing the above polysiloxane in an amount of 0.01 to 99% by weight together with a basic substance or basic polysaccharide and the above porous particulate or chitosan as a deodorant.
  • the above polysiloxane have a melting point of 60 to 140°C, that the polysiloxane have alkyl groups of at least 16 carbon atoms on the average at both its molecular terminals, and that the proportion of the sum total of the alkyl groups having at least 16 carbon atoms on the average in the polysiloxane having said alkyl groups be in the range of 0.5 to 40% by weight.
  • the amphoteric porous particulate of the present invention can be obtained by emulsifying or suspending an aqueous solution containing a basic polysaccharide and an organic acid having a reactive vinyl group in a hydrophobic solvent and thereafter effecting polymerization thereof.
  • the basic polysaccharide suitable for use in the present invention is a compound having such a structure that pyranose rings having primary or secondary amino groups are bonded through ether chains.
  • examples thereof include chitosan as a polyglucosamine, chitin as an acetylation product of chitosan, polygalactosamine, and an acetylation product thereof. Since a naturally occurring chitin generally contains, in part, free amino groups, i.e. non-acetylated groups, the chitin for use in the present invention has a degree of de-acetylation of less than 30%, while the chitosan for use in the present invention has a degree of de-acetylation of at least 30%.
  • This basic polysaccharide includes ones partially modified by such reactions as acylation, etherification and esterification.
  • the present invention is characterized by the formation of a porous structure, so that the use of chitosan is preferred.
  • the molecular weight of the basic polysaccharide is not particularly limited, ones having a molecular weight of about ten thousand to one million are generally employed.
  • a water-soluble organic acid capable of dissolving the basic polysaccharide to thereby provide an aqueous solution and having in its molecule at least one reactive vinyl group and at least one acid group may be mentioned as the organic acid having a reactive vinyl group suitable for use in the present invention.
  • Examples thereof include unsaturated carboxylic acid monomers such as acrylic, methacrylic, crotonic, itaconic and maleic acids; unsaturated sulfonic acid monomers such as styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-sulfopropyl (meth)acrylate and bis(3-sulfopropyl) itaconate; and unsaturated phosphoric acid monomers such as vinylphosphonic acid, vinyl phosphate, bis(methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate and dioctyl-2-(meth)acryloyloxyethyl phosphate.
  • the organic acid is used in a molar amount of 0.1 to 500 times, preferably 0.5 to 10 times the number of moles of monosaccharide units composing the basic polysaccharide. From the viewpoint that the characteristics of the individual polymers are fully exhibited, it is especially preferred that the organic acid be used in a molar amount of 1.0 to 5 times the number of moles of monosaccharide units.
  • the above organic acid having a reactive vinyl group may be arbitrarily mixed with various types of acids.
  • miscible acids include inorganic acids such as hydrochloric, sulfuric and phosphoric acids; and organic acids such as formic, acetic, lactic, citric, tartaric, succinic, malic, oxalic, glycolic, dichloroacetic and trifluoroacetic acids.
  • copolymerization may be effected with the use of another monomer which is copolymerizable with the organic acid having a reactive vinyl group.
  • another monomer which is copolymerizable with the organic acid having a reactive vinyl group.
  • unsaturated acid esters, organic acid vinyl esters and aromatic vinyl monomers may be mentioned as such other copolymerizable monomers.
  • water-soluble monomers which can be synthesized by the W/O type polymerization are preferred, examples of which include unsaturated acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate; organic acid vinyl esters such as vinyl acetate and vinyl propionate; and aromatic vinyls such as vinylpyridine.
  • a compound having a reactive group may be added to the reaction system, if it is capable of reacting with the acid group of the organic acid having a reactive vinyl group.
  • a chain transfer agent and a terminator may be added to the reaction system.
  • the emulsion or suspension polymerization may be carried out in the presence or absence of a surfactant. It is preferred that the polymerization be effected in the presence of a surfactant.
  • a surfactant Conventional anionic, nonionic, cationic and amphoteric surfactants may be used in the present invention.
  • an anionic surfactant such as dodecyl sulfate, dodecyl benzenesulfonate or polyoxyethylene nonylphenyl ether sulfate
  • a cationic surfactant such as octadecyltrimethylammonium chloride
  • a nonionic surfactant such as polyoxyethylene dodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene nonylphenyl ether, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate or polyoxyethylene sorbitan monolaurate
  • an amphoteric surfactant such as alkyldimethylaminoacetic acid betaine, alkylamidodimethylaminoacetic acid betaine or 2-alkyl-N-carboxy-N-hydroxyimidazolinium betaine.
  • hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane and cyclohexane
  • aromatics such as toluene and benzene
  • ethers such as petroleum ether and diethyl ether
  • halogenated hydrocarbons
  • the reaction be conducted in the above hydrophobic solvent after the above surfactant has been dissolved therein.
  • the surfactant concentration of the hydrophobic solvent is preferred to be in the range of 0.1 to 10.0% by weight, especially 0.5 to 5.0% by weight.
  • a water-soluble polymer which acts as an emulsifying agent or protective colloid and is effective in stabilizing the particles, such as hydroxyethylcellulose, polyvinyl alcohol, cationic polyvinyl alcohol having a quaternary salt group incorporated therein, anionic polyvinyl alcohol having a carboxylic acid or sulfonic acid group incorporated therein, starch or cationic starch having a quaternary salt group incorporated therein.
  • the polymerization initiator for use in the present invention is generally used water- or oil-soluble peroxodisulfates, peroxides and azobis compounds which undergo free-radical decomposition under heating or in the presence of a reducing substance to thereby initiate the addition polymerization of a monomer.
  • a peroxide such as potassium persulfate, ammonium persulfate, hydrogen peroxide or t-butyl hydroperoxide
  • an azo compound such as 2,2'-azobis-2-amidinopropane salt (V-50) or 4,4'-azobis-4-cyanopentanoic acid may be used as the initiator.
  • the initiator may be combined with a reducing agent to use the same as a redox initiator.
  • the above polymerization initiators may be used either individually or in combination.
  • the polymerization initiator may be added to an acidic aqueous solution of an organic acid of a basic polysaccharide. Alternatively, it may directly be added to an emulsion system.
  • the polymerization initiator may be used in an amount of 0.05 to 10.0% by weight based on the organic acid.
  • a chain transfer agent such as a mercaptan compound and a pH buffer such as sodium carbonate may be used in the polymerization according to the present invention.
  • an acidic aqueous solution of an organic acid of a basic polysaccharide is mixed with a hydrophobic solvent to which a surfactant has been added, followed by mechanical agitation with the use of an emulsifier to thereby effect emulsification.
  • a W/O emulsion is prepared.
  • a homogenizer, a high-pressure homogenizer, a milder, a homomixer, an ultrasonic emulsifier, a nanomizer system or a glass membrane-emulsifier may be used as the emulsifier.
  • a W/O suspension may be prepared from an acidic aqueous solution of an organic acid of a basic polysaccharide and a hydrophobic solvent to which a surfactant has been added, which suspension is directly subjected to polymerization reaction.
  • the mixing ratio of the acidic aqueous solution of an organic acid of a basic polysaccharide to the hydrophobic solvent at the time of emulsification/suspension may be freely selected as long as it is within the range of 70/30 to 0.1/99.9 on the volume basis.
  • a polymerization initiator is added to the prepared W/O emulsion or suspension of a basic polysaccharide, and polymerization is effected at 20 to 80°C. The polymerization is completed within a period of 0.1 to 24 hours. The resultant mixture is cooled and dropped into or added at once to an organic solvent to thereby precipitate a porous particulate.
  • the obtained particulate is treated by filtration, centrifugation or the like to thereby separate a solid from a liquid.
  • the solid is repetitively washed with an alcohol or the like and dried, thereby obtaining a powdery particulate.
  • organic solvents examples include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, heptanol and octanol; polar solvents such as acetone, acetonitrile, tetrahydrofuran, dioxane and ethyl acetate; and nonpolar solvents such as cyclohexane, hexane, heptane and octane.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, heptanol and octanol
  • polar solvents such as acetone, acetonitrile, tetrahydrofuran, dioxane and ethyl acetate
  • nonpolar solvents such as cyclohexane, hexane, heptane and oc
  • a base be added to the organic solvent.
  • the bases suitably added include amines such as ammonia, methylamine, ethylamine, propylamine, butylamine, isobutylamine, hexylamine, octylamine, amino-modified silicone, ethylenediamine, propylenediamine and butylenediamine; and alkaline substances such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium alkoxides and potassium alkoxides.
  • the base is added in an amount of preferably 0.1 to 2.0 mol.%, still preferably 0.8 to 1.2 mol.% based on the organic acid polymer of the particulate.
  • the porous particulate may include in its body an inorganic substance such as ZnO or MgO, a basic substance such as arginine, a lipophilic substance such as cyclic silicone, triglyceride or squalene, and a perfume.
  • an inorganic substance such as ZnO or MgO
  • a basic substance such as arginine
  • a lipophilic substance such as cyclic silicone, triglyceride or squalene
  • a perfume such as cyclic silicone, triglyceride or squalene
  • the amphoteric porous particulate of the present invention has an average particle size of 50 ⁇ m or less.
  • the average particle size is generally at least 0.01 ⁇ m and preferably ranges from 0.1 to 30 ⁇ m.
  • the average particle size is greater than 50 ⁇ m, the amount of the basic and acid group capable of reacting with strong acids and bases per particle is so reduced as to lower the adsorptive effect of the particulate.
  • the average particle size is one determined by measuring a 1% by weight ethanol solution of the polymer particulate at room temperature by the use of a laser diffraction particle size distribution meter (LA-100 manufactured by Horiba).
  • the configuration of the amphoteric porous particulate of the present invention is not particularly limited; it is preferred that the particulate be composed of spherical particles from the viewpoint that the feel is excellent at the application of the particulate to the skin.
  • the amphoteric porous particulate of the present invention has a specific surface area of 10 to 300 m 2 /g.
  • the specific surface area range from 20 to 200 m 2 /g, especially from 25 to 150 m 2 /g.
  • the specific surface area is one determined in accordance with the BET one-point method by the use of an automatic flow-type specific surface area meter (Flow Sorb model 2300 manufactured by Shimadzu Corp.).
  • a large specific surface area means that the particulate is porous.
  • the chitosan particulate suitable for use in the present invention may be prepared by heating chitin as a substance constituting the mantle of a crustacean such as a lobster, a crab or an insect in a 30 to 50% by weight aqueous alkali solution at 60°C or higher to thereby effect de-acetylation and atomizing the obtained chitosan particulate by a given method.
  • Various methods are available for atomizing the chitosan, which include, for example, a method (1) in which an acidic aqueous solution of chitosan is dropped into an aqueous alkali solution through a nozzle, a method (2) in which an acidic aqueous solution of chitosan is formed and sprayed into a high-temperature atmosphere and dried, and a method (3) in which an acidic aqueous solution of chitosan is mixed with a hydrophobic solvent and emulsified to thereby form an emulsion, which is poured into a base or an organic solvent to thereby coagulate the chitosan (emulsification process).
  • the method (3) is preferred because a chitosan particulate whose available amino group content and specific surface area are large and which has a regulated configuration can be obtained.
  • the particulate may be composed of particles each of which is spherical, amorphous or nonspherical but having a definite shape.
  • a chitosan particulate composed of spherical particles is preferred because an excellent feel is provided at the time of application to the skin.
  • nonspherical but having a definite shape refers to a shape having an uneven structure obtained by shrinkage and deformation of a ball. For example, it means not spherical but definite shape such as a red blood cell, cap or golf ball shape.
  • the cap shape is obtained by monoaxial monodirectional shrinkage and deformation of a hollow ball, while the red blood cell shape is obtained by monoaxial bidirectional shrinkage thereof.
  • Multiaxial multidirectional shrinkage and deformation of a hollow ball gives a tridirectionally uneven shape or a golf ball shape.
  • an acid for use in such an acidic aqueous solution may be inorganic acids such as hydrochloric, sulfuric and phosphoric acids; and organic acids such as formic, acetic, lactic, citric, tartaric, succinic, malic, oxalic, glycolic, dichloroacetic and trifluoroacetic acids.
  • organic acids such as formic, acetic, lactic, citric, tartaric, succinic, malic, oxalic, glycolic, dichloroacetic and trifluoroacetic acids.
  • tartaric, succinic, malic and glycolic acids are preferred from the viewpoint of solubility, stability and smell.
  • a water-soluble organic acid having in its molecule a reactive vinyl group, especially at least one reactive vinyl group may be used in the above acidic aqueous solution.
  • water-soluble organic acids examples include unsaturated carboxylic acid monomers such as acrylic, methacrylic, crotonic, itaconic and maleic acids; unsaturated sulfonic acid monomers such as styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-sulfopropyl (meth)acrylate and bis-(3-sulfopropyl)-itaconate; and unsaturated phosphoric acid monomers such as vinylphosphonic acid, vinyl phosphate, bis-(methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate and dioctyl-2-(meth)acryloyloxyethyl
  • the acidic aqueous solution of chitosan is generally prepared by gradually adding chitosan to an aqueous solution of the above acid heated at 50 to 70°C while stirring to thereby dissolve the chitosan.
  • the acid concentration of the aqueous solution is not particularly limited as long as chitosan is soluble therein.
  • the chitosan concentration is also not particularly limited, 1 to 10% by weight is preferred from the viewpoint of the viscosity.
  • a nonionic surfactant is preferably employed as the emulsifying agent in the emulsification.
  • suitable nonionic surfactants include sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene lauryl alcohol ether and polyoxyethylene cetyl alcohol ether. These emulsifying agents may be used either individually or in combination.
  • the hydrophobic solvent to be employed for dissolving the above emulsifying agent may be selected from among, for example, hydrocarbons such as hexane and cyclohexane; aromatics such as toluene and benzene; ethers such as petroleum ether and diethyl ether; and halogenated hydrocarbons such as chloroform and carbon tetrachloride.
  • the emulsifying agent concentration of the hydrophobic solvent is suitable to be in the range of 0.1 to 10.0% by weight, preferably 0.5 to 5.0% by weight.
  • a W/O emulsion of an acidic aqueous solution of chitosan is produced by adding a hydrophobic solvent containing an emulsifying agent to an acidic aqueous solution of chitosan and by conducting mechanical agitation with the use of an emulsifier to thereby effect emulsification.
  • a homogenizer, a high pressure homogenizer, a milder, a homomixer, a touch mixer, an ultrasonic emulsifier, a nanomizer system or a glass-membrane emulsifier may be used as the emulsifier.
  • the mixing ratio of the acidic aqueous solution of chitosan to the hydrophobic solvent containing an emulsifying agent is preferred to range from 9/1 to 1/9, especially from 7/3 to 3/7 on the volume basis.
  • one composed of spherical particles may be obtained by pouring the above-prepared W/O emulsion of an acidic aqueous solution of chitosan in an organic solvent per se or an organic solvent containing a base to thereby coagulate and precipitate the chitosan while maintaining the spherical shape thereof.
  • an organic solvent per se When an organic solvent per se is employed in the coagulation and precipitation of a chitosan emulsion, it is preferably used alcohols such as methanol, ethanol, propanol, isopropanol, butanol and octanol; polar solvents such as acetone, acetonitrile, tetrahydrofuran, dioxane and ethyl acetate; and nonpolar solvents such as cyclohexane and hexane.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol and octanol
  • polar solvents such as acetone, acetonitrile, tetrahydrofuran, dioxane and ethyl acetate
  • nonpolar solvents such as cyclohexane and hexane.
  • the organic solvent is preferably used alcohols such as methanol, ethanol, propanol, isopropanol and butanol; polar solvents such as acetone, acetonitrile, tetrahydrofuran, dioxane and ethyl acetate; and nonpolar solvents such as cyclohexane and hexane.
  • alcohols having 4 or less carbon atoms and polar solvents such as acetone, acetonitrile, tetrahydrofuran, dioxane and ethyl acetate are preferred.
  • Suitable bases include amines such as ammonia, methylamine, ethylamine, propylamine, butylamine, isobutylamine, hexylamine, octylamine, amino-modified silicone, ethylenediamine, propylenediamine and butylenediamine; and alkaline substances such as sodium hydroxide, potassium hydroxide and calcium hydroxide.
  • sodium hydroxide, potassium hydroxide, butylamine, hexylamine and octylamine are preferred.
  • butylamine, hexylamine and octylamine are especially preferred because a chitosan particulate composed of particles having an increased sphericity can be obtained.
  • the amount of the coagulation fluid depends on the type of the coagulation fluid, it is generally 2 to 50 times the volume of the emulsion.
  • a W/O emulsion containing chitosan When a W/O emulsion containing chitosan is dropped into the above coagulation fluid under agitation, the chitosan is coagulated and precipitated in the form of spherical particles.
  • the spherical particles of chitosan are collected by filtration or centrifugation, satisfactorily washed with an alcohol or the like, and dried. Thus, a chitosan particulate composed of spherical particles is obtained.
  • one composed of particles each being nonspherical but having a definite shape may be obtained by employing a solution of a mixture of an amine and an alcohol as the above coagulation fluid.
  • suitable amines include ammonia; primary amines each having an alkyl chain of about 1 to 12 carbon atoms; secondary amines such as diethylamine, diisobutylamine and diisopropylamine; tertiary amines such as triethylamine and tri-n-octylamine; diamines such as ethylenediamine, propylenediamine and butylenediamine; amino alcohols such as monoethanolamine, diethanolamine and triethanolamine; heterocyclic amines such as pyridine and pyrrole; and polyethyleneimine, amino-modified acrylic polymer and amino-modified silicone.
  • amines which are not completely miscible with water and rather only slightly soluble in water can be suitably employed.
  • amines each having an alkyl group of 2 to 12 carbon atoms especially monoalkylamines or primary amines each having an alkyl group of 4 to 12 carbon atoms, secondary amines each having an alkyl group of 3 to 10 carbon atoms, tertiary amines each having an alkyl group of 2 to 8 carbon atoms and amino-modified silicone, still especially amino-modified silicone.
  • the alcohol suitable for use in the present preparation is, for example, a monoalcohol having an alkyl group of about 1 to 20 carbon atoms, of which a monoalcohol having an alkyl group of 4 to 12 carbon atoms such as butanol, isobutyl alcohol, hexanol, heptanol or octanol is preferred.
  • the employed amine is amino-modified silicone, isobutyl alcohol and butanol are especially preferred.
  • the employed amine is a primary amine such as n-butylamine, a monoalcohol having 6 to 12 carbon atoms is especially preferred.
  • the mixing ratio of the amine to the alcohol in the solution of a mixture of an amine and an alcohol is not particularly limited, it is preferred to range from 2/3 to 8/2 on the volume basis when amino-modified silicone is used as the amine.
  • the volume ratio exceeds 8/2, the configuration of the resultant particulate is an agglomerate of fine particles each being nonsherical but having a definite shape, so that dispersed particles cannot be obtained.
  • the volume ratio is less than 2/3, the resultant particulate is composed of spherical particles although dispersed fine particles are obtained, so that fine particles each nonspherical but having a definite shape cannot be obtained.
  • the coagulation temperature is not particularly limited as long as it is not higher than the boiling points of the coagulation fluid and the hydrophobic solvent and water of the emulsion.
  • the configuration of the particulate can be regulated by the coagulation temperature.
  • the coagulation temperature at 20 to 50°C produces particles each in tridirectionally uneven definite form while at 50°C or higher produces particles each in red-blood-cell-shaped or cap-shaped definite form.
  • the coagulation fluid is generally employed in an amount of 2 to 50 times the volume of the emulsion although it depends on the type of the coagulation fluid, etc.
  • the chitosan particulate to be used herein includes various forms of chitosan particulates such as a chitosan particulate having undergone a chemical modification such as partial acetylation, a crosslinked chitosan particulate obtained by crosslinking with an epoxy group and the like, a coated chitosan particulate obtained, for example, by emulsion polymerization with the use of chitosan as protective colloid, a composite chitosan particulate obtained by combination with organic or inorganic powder, and a chitosan/vinyl polymer composite particulate obtained by reversed-phase suspension polymerization.
  • the chitosan particulate of the present invention has an average particle size of 0.01 to 50 ⁇ m, preferably 0.1 to 30 ⁇ m and still preferably 1 to 30 ⁇ m.
  • the average particle size is greater than 50 ⁇ m, rough touch results in the application thereof to the skin to thereby give bad feel.
  • the average particle size is less than 0.01 ⁇ m, unfavorably, the blending becomes difficult and creaky touch results in the application thereof to the skin.
  • the average particle size is one determined by measuring a 1% by weight ethanol solution of the chitosan particulate at room temperature by the use of a laser diffraction particle size distribution meter (LA-100 manufactured by Horiba).
  • the chitosan particulate of the present invention have an available amino group content of 1.0 ⁇ 10 -7 to 1.0 ⁇ 10 -2 mol/g, especially 1.0 ⁇ 10 -5 to 1.0 ⁇ 10 -2 mol/g, from the viewpoint that a satisfactory deodorant effect is attained.
  • available amino group content of the chitosan particulate (mol/g) refers to the number of moles of the amino groups capable of forming salts with carboxylic acids per unit weight of the chitosan particulate.
  • the specific surface area of the chitosan particulate of the present invention is preferred to range from 10 to 300 m 2 /g, especially from 30 to 300 m 2 /g, and still especially 50 to 300 m 2 /g from the viewpoint that a satisfactory deodorant effect is attained.
  • the specific surface area is one determined in accordance with the BET one-point method by the use of an automatic flow-type specific surface area meter (Flow Sorb model 2300 manufactured by Shimadzu Corp.).
  • a large specific surface area means that the particulate is porous.
  • the chitosan particulate of the present invention have a weight-average molecular weight of 1 ⁇ 10 3 to 1 ⁇ 10 6 .
  • This molecular weight is one determined by GPC with the use of a 0.5 M acetate buffer (0.5 M acetic acid + 0.5 M sodium acetate) as an eluent in a water-base column.
  • the molecular weight is one calculated in terms of PEG.
  • the degree of de-acetylation of the chitosan particulate of the present invention is preferred to be at least 80% from the viewpoint that a satisfactory deodorant effect is attained.
  • the degree of de-acetylation is one determined by colloid titration in which an acidic aqueous solution of chitosan is titrated with potassium polyvinylsulfate with the use of toluidine blue as the indicator.
  • Another method may be employed in which 8-anilino-1-naphthalene-sulfonate is used as the indicator so as to form a chitosan-indicator complex, followed by fluorometry.
  • the polysiloxane for use in the present invention has alkyl groups of at least 16 carbon atoms on the average as the side chains or at both its molecular terminals.
  • the number of carbon atoms and the molecular weight of each of the alkyl chains are not particularly limited as long as the melting point of the polysiloxane is 20°C or above. When the melting point is lower than 20°C, it is melted by the skin temperature in the application to the skin, thereby becoming oily, likely to flow down and sticky and having a less tendency to remain on the skin, so that the active ingredients of the deodorant cannot be persistently held on the skin.
  • the long-chain alkyl group means an alkyl group whose average number of carbon atoms is at least 16.
  • the average number of carbon atoms is preferably at least 30, still preferably in the range of 40 to 70.
  • the polysiloxane especially preferred in the present invention has a melting point of 60 to 140°C, contains long-chain alkyl groups at both its molecular terminals, and has a structure represented by the following general formula (I).
  • n is the average number of carbon atoms of the long-chain alkyl groups, satisfying the relationship: (n + 1) ⁇ 30; and m is a number of 0 or above, although not particularly limited, preferably ranges from 100 to 5000, because when it is 100 or above, the coating film has excellent moisture permeability and flexibility.
  • the blendability of the compound is good in view of viscosity of 5,000 or less. From the same viewpoint, m is especially preferred to range from 200 to 5000.
  • the polysiloxane for use in the present invention can be produced by reacting a 1-olefin with polydimethylsiloxane having silicon-hydrogen bonds in the presence of a catalyst such as platinum.
  • a catalyst such as platinum.
  • the polysiloxane represented by the above general formula (I) and having long-chain alkyl groups at both its molecular terminals may be obtained by reacting a 1-olefin with a polysiloxane having hydrogen atoms at both its molecular terminals as the starting material in the presence of a catalyst such as platinum, the molecular weight of the 1-olefin as the starting material is limited, so that it is difficult to obtain a long-chain-alkyl-modified polydimethylsiloxane having a melting point as high as, for example, 60°C or above. Further, if a 1-olefin of high molecular weight is employed, it is difficult to remove remaining 1-olefin and catalyst.
  • the above synthetic method is not preferable.
  • the polysiloxane represented by the above general formula (I) and having long-chain alkyl groups at both its molecular terminals be synthesized by the long-chain-alkyl-modified polysiloxane synthesizing process discovered by the inventors and disclosed in the specification of Japanese Patent Application No. 69478/1994. More specifically, a living polyethylene obtained by the living polymerization of ethylene is reacted with a cyclic siloxane, followed by the polymerization of a cyclic polydimethylsiloxane, a chain polydimethylsiloxane having a silanol group at its terminal or a mixture thereof in the presence of a catalyst.
  • polydimethylsiloxane having long-chain alkyl groups at both its molecular terminals can be synthesized at a high reproducibility.
  • the synthesized polysiloxane having long-chain alkyl groups at both its molecular terminals can stand the flow down during a high-temperature season and fix the active ingredients of the deodorant on the skin for a prolonged period of time by virtue of the presence of crystalline alkyl groups of high melting point at both its molecular terminals. Further, the polysiloxane has such characteristics that, since the long-chain alkyl groups are present only at both the terminals, a siloxane portion ensuring high permeabilities to gases and steam is secured in the molecule at a high ratio, so that the cutaneous respiration and skin drying are not blocked. Therefore, the above polysiloxane having long-chain alkyl groups only at both its molecular terminals is especially preferred in the present invention.
  • the cosmetic of the present invention contains the amphoteric porous particulate obtained by the above processes.
  • the content of the amphoteric porous particulate in the cosmetic of the present invention is preferred to range from 0.1 to 70% by weight, especially from 10 to 60% by weight from the viewpoint of the deodorant effect and blend stability.
  • the cosmetic comprehends skin cosmetics such as antiperspirants, deodorants, packs and humectants, and hair care products. It is preferred that the composition of the present invention be used as a deodorant.
  • ingredients arbitrarily selected from among the conventional ones may be added to the cosmetic of the present invention.
  • ingredients include metallic oxides such as zinc and magnesium oxides; antiperspirant astringent agents such as aluminum hydroxychloride and zinc sulfocarbolate; bactericides such as isopropylmethylphenol, trichlorocarbanilide and Sanisol; platy and spherical powders such as talc, Amihope and nylon powder; solid and semisolid oils such as vaseline, ceresin, higher fatty acids and higher alcohols; fluid oils such as squalane, ester oil, diglyceride and silicone oil; water-soluble polymers such as sodium polyacrylate, polyvinyl alcohol and methylcellulose; organic acids such as lactic and succinic acids; humectants such as glycerol and sorbitol; antiphlogistics such as dipotassium glycyrrhizinate and allantoin; and
  • an oil capable of disparsing the amphoteric porous particulate be contained in the deodorant, and that the oil content of the deodorant range from 10 to 90% by weight.
  • the form in which the cosmetic of the present invention is used is not particularly limited.
  • it is used in the form of lotion, aerosol, powder, stick, cream, pack, soap or shampoo.
  • the content of the chitosan particulate in the deodorant of the present invention is preferred to range from 0.1 to 50% by weight, especially from 10 to 50% by weight, and still especially from 20 to 50% by weight.
  • ingredients arbitrarily selected from among the conventional ones may be added to the deodorant of the present invention.
  • ingredients include metallic oxides such as zinc and magnesium oxides; antiperspirants such as aluminum hydroxychloride and tannic acid; bactericides such as trichlorohydroxydiphenyl ether (triclosan), isopropylmethylphenol, trichlorocarbanilide and Sanisol; and masking agents such as perfumes.
  • ingredients which may be added to the deodorant of the present invention include oils such as dimethylsiloxane, silicone oils (e.g., volatile cyclic silicone), higher fatty acid esters, wax and higher alcohols (e.g., stearyl alcohol); humectants such as glycerol and sorbitol; surfactants such as metallic soaps (e.g., sodium stearate) and nonionic surfactants (e.g., sorbitan fatty acid ester); antiseptics such as methylparaben, butylparaben and propylparaben; powder such as nylon powder and talc; antiphlogistics such as dipotassium glycyrrhizinate, allantoin and guaiazulene; thickeners such as polysodium acrylate, polyvinyl alcohol, methylcellulose, bentonite and hectorite; coloring matters such as Green No. 3, Blue No. 1, Yellow No. 4 and Yellow No
  • the form in which the deodorant of the present invention is used is not particularly limited.
  • it is used in the form of lotion, aerosol, powder, stick or cream.
  • the proportion of the long-chain alkyl portions of the polysiloxane having long-chain alkyl groups and a melting point of 20°C or higher for use in the present invention be in the range of 0.5 to 40% by weight, especially 1 to 40% by weight.
  • this proportion exceeds 40% by weight, the resultant film would have degraded moisture permeability and flexibility.
  • the proportion is less than 0.5% by weight, the film would easily flow down by sebum or the like, would be sticky, and would have difficulty in remaining on the skin especially at high temperatures.
  • the polysiloxane having long-chain alkyl groups and a melting point of 20°C or higher is blended in the deodorant of the present invention in an amount of 0.01 to 99% by weight, preferably 1 to 70% by weight, although it depends on the use and blend forms.
  • the amount is less than 0.01% by weight, the active ingredients of the deodorant cannot persistently be held on the skin, so that the deodorant effect cannot be persistent.
  • the amount exceeds 99% by weight, the amount of blended active ingredients becomes so small that it would become difficult to attain desirable deodorant effect.
  • ingredients arbitrarily selected from among the conventional one may be added to the above deodorant of the present invention, and the deodorant effect can be retained for a prolonged period of time even under such harsh conditions as high temperatures and sweating by persistently holding the ingredients on the skin.
  • added ingredients include astringent agents such as aluminum hydroxychloride and zinc phenolsulfonate; bactericides such as isopropylmethylphenol, trichlorocarbanilide and Sanisol; and powders such as talc, Amihope and nylon powder.
  • the deodorant of the present invention is endowed with a high deodorant effect by adding a basic substance to the same to thereby capture the organic acids causing body smells in the coating film.
  • basic substances include inorganic materials, for example, metallic oxides such as zinc and magnesium oxides and organic compounds having an amino group, such as chitosan.
  • the content of the basic substance in the deodorant of the present invention is preferred to be about 0.1 to 70% by: weight from the viewpoint of deodorant effect and blend stability.
  • the porous particulate described hereinbefore as the above basic substance be blended in the deodorant of the present invention, because a high deodorant effect can be retained for an extremely prolonged period of time.
  • the amphoteric porous particulate is dispersed in a flexible and hydrophobic film composed of the modified polysiloxane having long-chain alkyl groups and a melting point of 20°C or higher, and that oily organic acids are diffused into the film with the result that these are captured by the amphoteric porous particulate.
  • This hydrophobic film is resistant to sweat and moisture from outside and has high moisture permeability, so that a very excellent deodorant effect can be exerted especially in the application to regions consistently in an environment of high temperature and humidity, such as the axilla, foot, scruff of the neck and chest, or in the use during summertime swimming and other sports.
  • the above amphoteric porous particulate is obtained by emulsifying or suspending an aqueous solution containing a basic polysaccharide having an amino group, such as chitosan, and an organic acid monomer having a reactive vinyl group, such as methacrylic acid, in a hydrophobic solvent and effecting polymerization thereof.
  • a basic polysaccharide having an amino group such as chitosan
  • an organic acid monomer having a reactive vinyl group such as methacrylic acid
  • the content of the amphoteric porous particulate in the deodorant of the present invention is preferred to be about 0.1 to 70% by weight from the viewpoint of deodorant effect and blend stability.
  • ingredients such as a surfactant, an alcohol, water and oil materials may be added to the above deodorant of the present invention, the amount and method of addition are determined so as not to be detrimental to the effects of the present invention.
  • the above deodorant of the present invention may be obtained by mixing and agitating the polysiloxane having long-chain alkyl groups and a melting point of 20°C or higher and other ingredients, occasionally, it may be needed to effect heating and melting.
  • the above deodorant of the present invention may be used in the form of stick, spray, mist spray, roll-on, cream or milky lotion.
  • the porous particulate of the present invention is weakly acidic and weakly basic, thus being amphoteric. It is one obtained by internally crosslinking a basic polysaccharide with an acidic polymer. It has the capability of readily reacting with strong bases or acids in nonpolar and polar solvents to thereby capture the bases or acids in the porous particulate. Further, the porous particulate can retain its particulate form without being dissolved in various solvents having mutually different polarities.
  • the porous particulate of the present invention based on a natural material is excellent in safety because no crosslinking agents are employed, so that it finds applications not only in the field of cosmetics and perfumes, e.g., skin cosmetics (antiperspirants, deodorants, packs and humectants) and hair care products, but also in drugs. Moreover, it is useful in fiber treatments, paper coatings, cement additives, covering materials, bactericides/bacteriostats, and agricultural chemicals.
  • Fig. 1 is a graph in which the residual 4-phenylbutyric acid content (Y) is logarithmically plotted against the amount of 4-phenylbutyric acid added per gram of chitosan particulate (X) for calculating the available amino group content of the chitosan particulate obtained in Synthetic Example 1.
  • the resultant chitosan solution was mixed with a 1.0% by weight cyclohexane solution of sorbitan monolaurate in a ratio of 5:5 (volumetric ratio) and agitated at a great rate of 15,000 rpm by means of a homogenizer, thereby obtaining a W/O emulsion.
  • a polymerization reaction was effected at 70°C for two hours, and the reaction mixture was cooled to room temperature and dropped into ethanol in an amount of 5 times as many moles (by volume) under agitation. Agitation was continued for 30 min, and any agglomerate was removed by decantation. Immersion in ethanol and agitation followed by filtration through a Buchner funnel were conducted thrice. Then, vacuum drying was effected, thereby obtaining a particulate. The particle size and configuration of the obtained particulate are summarized and shown in Table 1.
  • a particulate was obtained in the same manner as in Example 1, except that 69.3 g of methacrylic acid (2 times the number of moles of the monosaccharide units of the chitosan) was used in place of 34.6 g of methacrylic acid.
  • the particle size and configuration of the obtained particulate are summarized and shown in Table 1.
  • a particulate was obtained in the same manner as in Example 1, except that 51.9 g of methacrylic acid (1.5 times the number of moles of the monosaccharide units of the chitosan) was used in place of 34.6 g of methacrylic acid.
  • the particle size and configuration of the obtained particulate are shown in Table 1.
  • a particulate was obtained in the same manner as in Example 1, except that 26.0 g of methacrylic acid (0.75 time the number of moles of the monosaccharide units of the chitosan) was used in place of 34.6 g of methacrylic acid.
  • the particle size and configuration of the obtained particulate are summarized and shown in Table 1.
  • a particulate was obtained in the same manner as in Example 1, except that 26.0 g of methacrylic acid (0.75 time the number of moles of the monosaccharide units of the chitosan) and 6 g of acetic acid (0.25 time the number of moles of the monosaccharide units of the chitosan) was used in place of 34.6 g of methacrylic acid.
  • the particle size and configuration of the obtained particulate are summarized and shown in Table 1.
  • a particulate was obtained in the same manner as in Example 1, except that 80 g of polygalactosamine (weight average molecular weight: 200,000) was used in place of chitosan.
  • the particle size and configuration of the obtained particulate are summarized and shown in Table 1.
  • a particulate was obtained in the same manner as in Example 1, except that a 5.0% by weight cyclohexane solution of sorbitan monolaurate was used in place of the 1.0% by weight cyclohexane solution of sorbitan monolaurate.
  • the particle size and configuration of the obtained particulate are summarized and shown in Table 1.
  • a particulate was obtained in the same manner as in Example 1, except that acrylic acid was used in place of methacrylic acid in an amount equimolar to the monosaccharide units of the chitosan.
  • the particle size and configuration of the obtained particulate are summarized and shown in Table 1.
  • a polymerization reaction was effected at 70°C for 3 hours in the same manner as in Example 4. Thereafter, the reaction mixture was cooled to room temperature and neutralized with a solution of 0.05 N (normality) aqueous NaOH/isopropanol (1/5 vol/vol) to a final pH of 9.0. Washing with isopropanol followed by filtration was conducted thrice, and vacuum drying was effected, thereby obtaining a particulate.
  • the particle size and configuration of the obtained particulate are summarized and shown in Table 1.
  • Particles were obtained in the same manner as in Comparative Example 1, except that acrylic acid was used in place of methacrylic acid in an amount equimolar to the monosaccharide units of the chitosan.
  • the particle size and configuration of the obtained particles are summarized and shown in Table 1.
  • Healthy males (aged 20 to 40) having strong axillary and foot smells were chosen and evaluated by organoleptic evaluations by four expert panelists. Specifically, first, the males having just arrived at office (around 9:00) had four expert panelists' organoleptic evaluations. Immediately after the evaluations, the deodorants prepared according to the following formulation examples were applied in appropriate amounts to the axillae and feet. Each male had the deodorant application at only one of the axillae and of the feet. The smells were evaluated just after the deodorant application and also in the evening before going home (around 16:00). None was applied to the other axilla and foot of each male to provide controls.
  • the evaluations involved four expert panelists, grading into any of the following six grades, the average of which was determined with respect to the axillary smell in Formulation Examples 1 to 5 while with respect to the foot smell in Formulation Example 6. Moreover, the results of evaluation of the formulation containing zinc oxide (specific surface area: 50 m 2 /g) in place of the amphoteric porous particulate of the present invention are shown in the Comparative Formulation Example.
  • the deodorant lotion of the following composition was prepared and applied to the axillae to evaluate the deodorant effect thereof.
  • the results are shown in Table 2.
  • the deodorant lotion of the following composition was prepared and applied to the axillae to evaluate the deodorant effect thereof.
  • the results are shown in Table 3.
  • the deodorant powder spray of the following composition was prepared and applied to the axillae to evaluate the deodorant effect thereof.
  • the results are shown in Table 4.
  • ⁇ Composition> Stock solution amphoteric porous spherical particulate (Ex. 9) 40.0% glycerol 5.0% isopropyl myristate 5.0% water 5.0% ethanol 45.0% in total 100.0% ⁇ Filling above stock solution 35.0% LPG gas 65.0% in total 100.0% Evaluation before appln. (ca 9:00) just after appln. before going home (ca 16:00) Invention product non-appln. part (control) 5 5 5 appln. part 5 1 3 Comp. product (zinc oxide) non-appln. part (control) 5 5 5 5 appln. part 5 4 4 4
  • the deodorant gel of the following composition was prepared and applied to the axillae to evaluate the deodorant effect thereof.
  • the results are shown in Table 5.
  • ⁇ Composition> amphoteric porous spherical particulate (Ex. 9) 40.0% carboxyvinyl polymer 1.0% propylene glycol 10.0% triethanolamine 1.0% ethanol 30.0% water 18.0% in total 100.0% Evaluation before appln. (ca 9:00) just after appln. before going home (ca 16:00) Invention product non-appln. part (control) 5 5 5 appln. part 5 2 3 Comp. product (zinc oxide) non-appln. part (control) 5 5 5 5 appln. part 5 4 4 4
  • the deodorant cream of the following composition was prepared and applied to the axillae to evaluate the deodorant effect thereof.
  • the results are shown in Table 6.
  • the deodorant powder spray of the following composition was prepared and applied to the feet to evaluate the deodorant effect thereof.
  • the results are shown in Table 7.
  • ⁇ Composition> Stock solution amphoteric porous spherical particulate (Ex. 9) 20.0% amphoteric porous spherical particulate (Ex. 2) 10.0% talc 20.0% aluminum hydroxychloride 2.0% isopropyl myristate 3.0% cetanol 15.0% dimethylpolysiloxane 30.0% in total 100.0% ⁇ Filling above stock solution 8.0% LPG gas 92.0% in total 100.0% Evaluation before appln. (ca 9:00) just after appln. before going home (ca 16:00) Invention product non-appln. part (control) 5 5 5 appln. part 5 1 2 Comp. product (zinc oxide) non-appln. part (control) 5 5 5 appin. part 5 4 4
  • the available amino group content was calculated by the following method. Further, in the Examples, the deodorant effect test with respect to the axillary and foot smells was conducted by the method described below.
  • Healthy males (aged 20 to 40) having strong axillary and foot smells were chosen and evaluated by organoleptic evaluations by four expert panelists. Specifically, first, the males having just arrived at office (around 9:00) had four expert panelists' organoleptic evaluations. Immediately after the evaluations, the deodorants prepared according to the following formulation examples were applied in appropriate amounts to the axillae and feet. Each male had the deodorant application at only one of the axillae and of the feet. The smells were evaluated just after the deodorant application. None was applied to the other axilla and foot of each male to provide controls.
  • the evaluations involved four expert panelists, grading into any of the following six grades, the average of which was determined with respect to the axillary smell in Examples 10 to 18 while with respect to the foot smell in Examples 19 and 20. Moreover, the results of evaluation of the formulation containing zinc oxide in place of the chitosan particulate are shown as the Comparative Example.
  • This acidic aqueous chitosan solution was mixed with a 2.0% toluene solution of sorbitan monolaurate in a ratio of 1:1 (volumetric ratio) and agitated at a great rate of 10,000 rpm by means of a homogenizer, thereby obtaining a W/O emulsion.
  • a chitosan particulate was obtained.
  • the obtained chitosan particulate was composed of perfectly spherical particles and had an average particle size of 10 ⁇ m.
  • FIG. 1 A graph is shown in Fig. 1 in which the residual 4-phenylbutyric acid content (Y) was logarithmically plotted against the amount of 4-phenylbutyric acid added per gram of chitosan particulate (X) for calculating the available amino group content of the obtained chitosan particulate.
  • the available amino group content of the obtained chitosan particulate and other properties are shown in Table 9.
  • chitosan 80 g of commercially available chitosan (SK-10 used in Synthetic Example 1) was dispersed in water. Then, 50 g of tartaric acid was added and dissolved while stirring at 60°C. Thus, an 8.0% aqueous solution of chitosan and tartaric acid was obtained.
  • This acidic aqueous chitosan solution was mixed with a 5.0% cyclohexane solution of sorbitan monolaurate in a ratio of 1:1 (volumetric ratio) and agitated at a great rate of 15,000 rpm by means of a homogenizer, thereby obtaining a W/O emulsion.
  • a chitosan particulate was obtained.
  • the obtained chitosan particulate was composed of particles each being nonspherical but having a definite form featured by unevenness along at least three directions and had an average particle size of 20 ⁇ m.
  • chitosan 78 g of commercially available chitosan (SK-10 used in Synthetic Example 1) was dispersed in water. Then, 50 g of tartaric acid was added and dissolved while stirring at 60°C. Thus, a 7.8% aqueous solution of chitosan and tartaric acid was obtained. Separately, 0.2 g of alumina (5% relative to chitosan) was dispersed in 5 ml of water. This alumina dispersion was dispersed in 50 ml of the acidic aqueous chitosan solution.
  • This acidic aqueous chitosan solution having the alumina powder dispersed therein was mixed with a 2.0% cyclohexane solution of sorbitan monolaurate in a ratio of 5:5 (volumetric ratio) and agitated at a great rate of 15,000 rpm by means of a homogenizer, thereby obtaining a W/O emulsion.
  • a chitosan particulate was obtained.
  • the obtained chitosan particulate was composed of perfectly spherical particles and had an average particle size of 20 ⁇ m.
  • Example 10 deodorant lotion (ethanol base)
  • the deodorant lotion of the following composition was produced, and the deodorant effect thereof was tested with respect to the axillary smell.
  • the results are shown in Table 10.
  • Example 11 deodorant lotion (volatile silicone base)
  • the deodorant lotion of the following composition was produced, and the deodorant effect thereof was tested with respect to the axillary smell.
  • the results are shown in Table 11.
  • the deodorant stick of the following composition was produced, and the deodorant effect thereof was tested with respect to the axillary smell.
  • the results are shown in Table 12.
  • the O/W-cream deodorant of the following composition was produced, and the deodorant effect thereof was tested with respect to the axillary smell.
  • the results are shown in Table 16.
  • Example 17 creamy (O/W-cream) deodorant
  • the O/W-cream deodorant of the following composition was produced. and the deodorant effect thereof was tested with respect to the axillary smell.
  • the results are shown in Table 17.
  • the W/O-cream deodorant of the following composition was produced, and the deodorant effect thereof was tested with respect to the axillary smell.
  • the results are shown in Table 18.
  • the liquid-spray deodorant of the following composition was produced, and the deodorant effect thereof was tested with respect to the foot smell.
  • the results are shown in Table 19.
  • ⁇ Composition of liquid-spray deodorant> Stock solution chitosan particulate (Synth. Ex. 1, av. particle size: 10 ⁇ m) 12.5% isopropyl myristate 5.0% glycerol 5.0% water 5.0% ethanol 72.5% in total 100.0% Filling above stock solution 35.0% LPG gas 65.0% in total 100.0% Compsn. Evaluation before appln. (ca 9:00) just after appln. Invention product not appld. (control) 5 5 chitosan particulate (Synth. Ex. 1, av. particle size: 10 ⁇ m) 5 1 Comp. product not appld. (control) 5 5 zinc oxide 5 3
  • the powder-spray deodorant of the following composition was produced, and the deodorant effect thereof was tested with respect to the foot smell.
  • the results are shown in Table 20.
  • ⁇ Composition of powder-spray deodorant> Stock solution chitosan particulate (Synth. Ex. 2, av. particle size: 20 ⁇ m) 5.0% talc 46.5% myristic ester 25.0% dimethylsilicone 5.0% methylpolycyclosiloxane 18.5% in total 100.0% Filling above stock solution 8.0% LPG gas 92.0% in total 100.0% Compsn. Evaluation before appln. (ca 9:00) just after appln. Invention product not appld. (control) 5 5 chitosan particulate (Synth. Ex. 2, av. particle size: 20 ⁇ m) 5 1 Comp. product not appld. (control) 5 5 zinc oxide 5 3
  • Each of about 20 axillary smell test subjects had a cotton pat fitted in the axilla for one day, and the cotton pats were collected and immersed in methanol to thereby recover the smell (about 2 l).
  • the methanol was concentrated to about 60 ml and used as an axillary smell sample.
  • a filter paper of 70 mm in diameter was placed on the bottom of a 300-ml beaker and impregnated with 0.35 g of the above axillary smell sample. It was allowed to stand still at room temperature for 3 min, and 0.2 g of the deodorant of the following composition was spread thereover. It was allowed to stand still at room temperature for 2 min, and the same four expert panelists' six-level-grading evaluation as in Examples 10 to 20 was carried out with one having no deodorant applied thereto as a control. The same evaluation was carried out with the use of zinc oxide as the comparative item. The results are shown in Table 21.
  • Synthetic Example 6 (exemplary synthesis of polysiloxane modified with long-chain alkyl groups at both its terminals)
  • the resultant polymerization mixture was dropped under a nitrogen stream into a solution of 11.8 g of octamethylcyclotetrasiloxane in 10 ml of dry cyclohexane separately provided in a 1-l short-necked round-bottomed flask in advance. After the completion of the dropping, a reaction was conducted at 30°C for 1 hour, The reaction mixture was poured into 2 l of methanol, agitated for 1 hours and filtered in a vacuum to thereby collect the formed solids. The solids were dried in a vacuum oven at 50°C for 24 hr. Thus, a white waxy solid was obtained. The product yield was 12.0 g.
  • the signals assignable to the methyl group bonded to the silyl group, the methylene group bonded to the silyl group, the initiation terminal methyl group and the methylene group of the principal chain were observed at -0.05 ppm (singlet), 0.4 ppm (triplet), 0.8 ppm (triplet) and about 1.2 ppm, respectively.
  • the terminal silanol group introduction ratio was found to be 99% from the individual signal integral ratios.
  • the number of introduced siloxane units was 1.4 per ethylene terminal.
  • the signals assignable to the methyl group bonded to the silyl group, the methylene group bonded to the silyl group, the initiation terminal methyl group and the methylene group of the polyethylene chain were observed at -0.05 ppm (singlet), 0.4 ppm (triplet), 0.8 ppm (triplet) and about 1.2 ppm, respectively.
  • the weight ratio of the polyethylene moiety to the siloxane moiety was found to be 10 : 90 from the individual signal integration ratios.
  • a temperature-programmed DSC measurement showed that the melting point of the product (apex of endothermic peak) was 92°C.
  • compositions of Table 22 each in the form of a suspension were prepared with the use of the polysiloxanes obtained in the above Synthetic Examples 6 to 8 and also with the use of paraffin wax (melting point: 68°C, produced by Nippon Seiro Co., Ltd.) for comparison as wax components.
  • paraffin wax melting point: 68°C, produced by Nippon Seiro Co., Ltd.
  • Each of these suspension compositions was applied to a leather, and the surface thereof was rubbed with a leather at 37°C. The residual coating content was measured and the surface condition was observed. Further, each of the compositions was applied to a Cellophane film, and the moisture permeability (unit: g/m 2 -24hr/10 ⁇ m, calcium chloride used as moisture absorbent, measured at 25°C in 65% RH) was determined. The results are shown in Table 22.
  • Invention product Comp. product 1 2 3 4 Compsn. (wt.%) polysiloxane modified with long-chain alkyls at both terminals (Synth. Ex. 6) 10 - - - side-chain-alkyl-modified polysiloxane (Synth. Ex. 7) - 10 - - both-terminal-alkyl-modified polysiloxane (Synth. Ex. 8) - - 10 - paraffin wax (m.p.: 68°C, prepd.
  • the chitosan solution was mixed with a 1.0% by weight cyclohexane solution of sorbitan monolaurate in a ratio of 5:5 (volumetric ratio) and agitated at a great rate of 15,000 rpm by means of a homogenizer, thereby obtaining a W/O emulsion.
  • a polymerization reaction was effected at 70° C for 2 hours, and the reaction mixture was cooled to room temperature, dropped into ethanol in a molar (volumetric) proportion of 1:5 under agitation. Agitation was continued for 30 min, and any agglomerate was removed by decantation. Immersion in ethanol and agitation followed by filtration through a Buchner funnel were conducted thrice. Then, vacuum drying was effected, thereby obtaining a particulate.
  • the obtained particulate had an average particle size of 12 ⁇ m, was composed of perfectly spherical particles, and had a specific surface area of 50 m 2 /g.
  • a deodorant stick was prepared according to the composition of Table 23 with the use of the polysiloxane modified with long-chain alkyl groups at both its terminals which was synthesized in Synthetic Example 6 and the amphoteric porous particulate which was synthesized in Synthetic Example 9.
  • Deodorant sticks were prepared in the same manner as in Example 22 with the use of the same amounts of the side-chain-alkyl-modified polysiloxane synthesized in Synthetic Example 7 and both-terminal-alkyl-modified polysiloxane synthesized in Synthetic Example 8, respectively, in place of the polysiloxane modified with long-chain alkyl groups at both its terminals which was synthesized in Synthetic Example 6.
  • a deodorant stick was prepared in the same manner as in Example 22 with the use of the same amount of hybrid zinc oxide in place of the amphoteric porous particulate synthesized in Synthetic Example 9.
  • a deodorant stick was prepared in the same manner as in Example 22 with the use of the same amount Qf paraffin wax (melting point: 68°C, produced by Nippon Seiro Co., Ltd.) in place of the polysiloxane modified with long-chain alkyl groups at both its terminals which was synthesized in Synthetic Example 6.
  • Healthy males (aged 20 to 40) having strong axillary or foot smells were chosen and evaluated by organoleptic evaluations by four expert panelists. Specifically, the males had four expert panelists' organoleptic evaluations at 9 o'clock in the morning. Immediately after the evaluations, the deodorant sticks prepared in the above examples were applied in appropriate amounts to the axillae and feet. Each male had the deodorant application at only one of the axillae and of the feet. The smells were evaluated just after the deodorant application, 1 hour later and 8 hours later. Moreover, for comparison, similar evaluations were made with respect to each of the amphoteric porous particulate synthesized in Synthetic Example 9 and the hybrid zinc oxide alone. The evaluation involved four expert panelists' grading into any of the following six grades. Further, the appearance of each of the surfaces having the deodorant applied thereto was observed 8 hours after the application.
  • a stock solution was prepared according to the composition of Table 25 with the use of the polysiloxane modified with long-chain alkyl groups at both its terminals which was synthesized in Synthetic Example 6 and the amphoteric porous particulate which was synthesized in Synthetic Example 9. 10% by weight of the above stock solution and 90% by weight of LPG gas were fed into a spray can, thereby preparing a deodorant spray.
  • Ingreidents stock soln.
  • Amt. (wt.%) polysiloxane modified with long-chain alkyls at both terminals (Synth. Ex. 6) 25 amphoteric porous particulate (Synth. Ex. 9) 10 talc 10 isopropyl myristate 5 cetanol 15 octamethyltetracyclosiloxane 25 dimethylsilicone 10 in total 100
  • Deodorant sprays were prepared in the same manner as in Example 26 with the use of the same amounts of the side-chain-alkyl-modified polysiloxane synthesized in Synthetic Example 7 and the both-terminal-alkyl-modified polysiloxane synthesized in Synthetic Example 8, respectively, in place of the polysiloxane modified with long-chain alkyl groups at both its terminals which was synthesized in Synthetic Example 6.
  • a deodorant spray was prepared in the same manner as in Example 26 with the use of the same amount of hybrid zinc oxide in place of the amphoteric porous particulate synthesized in Synthetic Example 9.
  • a deodorant spray was prepared in the same manner as in Example 26 with the use of the same amount of paraffin wax (melting point: 68°C, produced by Nippon Seiro Co., Ltd.) in place of the polysiloxane modified with long-chain alkyl groups at both its terminals which was synthesized in Synthetic Example 6.

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Claims (27)

  1. Amphoteres poröses Teilchen, umfassend ein basisches Polysaccharid und ein Polymer einer organischen Säure mit reaktiver Vinylgruppe oder eines Salzes davon, welches eine Durchschnittsteilchengröße von 50 µm oder weniger aufweist.
  2. Poröses Teilchen gemäß Anspruch 1, das aus kugelförmigen Feinpartikeln zusammengesetzt ist.
  3. Poröses Teilchen gemäß Anspruch 1 oder 2, das eine spezifische Oberflächenfläche von 10 bis 300 m2/g aufweist.
  4. Poröses Teilchen gemäß Anspruch 1 oder 2, worin das basisches Polysaccharid Chitosan ist.
  5. Poröses Teilchen gemäß Anspruch 1 oder 2, worin die organische Säure mit reaktiver Vinylgruppe oder eines Salzes davon Methacrylsäure oder ein Salz davon sind.
  6. Verfahren zur Herstellung des in Anspruch 1 definierten porösen Teilchens, wobei man eine wässrige Lösung, enthaltend ein basisches Polysaccharid und eine organische Säure mit reaktiver Vinylgruppe, in einem hydrophoben Lösungsmittel emulgiert oder suspendiert und danach deren Polymerisation durchführt.
  7. Verfahren gemäß Anspruch 6 zur Herstellung eines porösen Teilchens, wobei, nach der Polymerisation, die Polymerisationsreaktionsmischung auf einmal in ein organisches Lösungsmittel gegossen oder zu diesem gegeben wird, welches eine Base enthält, um dadurch ein poröses Teilchen auszufällen.
  8. Verfahren gemäß Anspruch 6 oder 7 zur Herstellung eines porösen Teilchens, wobei die organische Säure in einer Menge vom 0,1 bis 500-Fachen der Zahl von Molen von Monosaccharid-Einheiten, aus denen das basisches Polysaccharid zusammengesetzt ist, verwendet wird.
  9. Kosmetische Zusammensetzung, dadurch gekennzeichnet, dass sie das in Anspruch 1 oder 2 definierte poröse Teilchen aufweist.
  10. Kosmetische Zusammensetzung gemäß Anspruch 9, die das amphotere Teilchen in einer Menge von 0,1 bis 70 Gew.% enthält.
  11. Kosmetische Zusammensetzung gemäß Anspruch 9, die ein Deodorant ist.
  12. Deodorant-Zusammensetzung, umfassend das in Anspruch 1 definierte poröse Teilchen und ein Öl mit der Befähigung zur Dispergierung des porösen Teilchens.
  13. Amphoteres poröses Teilchen gemäß Anspruch 1 aus kugelförmigen Feinpartikeln, welches ein basisches Polysaccharid und ein Polymer aus einer eine reaktive Vinylgruppe enthaltenden organischen Säure umfasst und eine Durchschnittspartikelgröße von 50 µm oder weniger aufweist.
  14. Poröses Teilchen gemäß Anspruch 1, worin das basische Polysaccharid Chitosan ist.
  15. Deodorant-Zusammensetzung, umfassend ein Chitosan-Teilchen mit einer Durchschnittspartikelgröße von 0,01 bis 50 µm als das deodorierende Mittel.
  16. Deodorant-Zusammensetzung gemäß Anspruch 15, worin das Chitosan-Teilchen eines spezifische Oberflächenfläche von 10 bis 300 m2/g aufweist.
  17. Deodorant-Zusammensetzung gemäß Anspruch 15 oder 16, worin das Chitosan-Teilchen einen verfügbaren Aminogruppen-Gehalt von 1,0 x 10-7 bis 1,0 x 10-2 Mol/g aufweist.
  18. Deodorant-Zusammensetzung gemäß Anspruch 15, worin das Chitosan-Teilchen aus kugelförmigen Feinpartikeln zusammengesetzt ist.
  19. Deodorant-Zusammensetzung, dadurch gekennzeichnet, dass sie das in Anspruch 1 definierte poröse Teilchen und 0,01 bis 99 Gew.% eines Polysiloxans mit Alkylgruppen von durchschnittlich mindestens 16 Kohlenstoffatomen als ein Öl umfasst, wobei das genannte Polysiloxan einen Schmelzpunkt von mindestens 20°C aufweist.
  20. Deodorant-Zusammensetzung gemäß Anspruch 15, die ferner 0,01 bis 99 Gew.% eines Polysiloxans mit Alkylgruppen von durchschnittlich mindestens 16 Kohlenstoffatomen und einem Schmelzpunkt von 20°C oder höher umfasst.
  21. Deodorant-Zusammensetzung, dadurch gekennzeichnet, dass sie ein deodorierendes Mittel und 0,01 bis 99 Gew.% eines Polysiloxans mit Alkylgruppen mit durchschnittlich mindestens 16 Kohlenstoffatomen an jedem der molekularen Enden und mit einem Schmelzpunkt im Bereich von 60 bis 140°C umfasst.
  22. Deodorant-Zusammensetzung gemäß Anspruch 21, dadurch gekennzeichnet, dass der Mengenanteil des langkettigen Alkylgruppen-Teils des Polysiloxans mit den langkettigen Alkylgruppen insgesamt im Bereich von 0,5 bis 40 Gew.% liegt.
  23. Deodorant-Zusammensetzung gemäß Anspruch 21, dadurch gekennzeichnet, dass sie eine basische Substanz umfasst.
  24. Deodorant-Zusammensetzung gemäß Anspruch 21, dadurch gekennzeichnet, dass sie ein amphoteres poröses Teilchen enthält, das ein basisches Polysaccharid und ein Polymer einer eine reaktive Vinylgruppe enthaltenden organischen Säure oder eines Salzes davon umfasst und eine Durchschnittspartikelgröße von 50 µm oder weniger aufweist.
  25. Deodorant-Zusammensetzung gemäß Anspruch 21, worin das Polysiloxan durch die allgemeine Formel (I) dargestellt ist:
    Figure 01120001
    worin n die Durchschnittszahl der Kohlenstoffatome der langkettigen Alkylgruppen, die die Beziehung (n + 1) ≥ 30 erfüllt, und m eine Zahl von 0 oder mehr sind.
  26. Zusammensetzung gemäß Anspruch 25, worin m eine Zahl von 100 bis 5000 ist.
  27. Verwendung eines in einem der Ansprüche 1 bis 5, 13 oder 14 definierten amphoteren porösen Teilchens als deodorierendes Mittel.
EP95912468A 1994-03-18 1995-03-17 Poröse feine teilchen und kosmetika Expired - Lifetime EP0803513B1 (de)

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Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5981719A (en) 1993-03-09 1999-11-09 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US6090925A (en) 1993-03-09 2000-07-18 Epic Therapeutics, Inc. Macromolecular microparticles and methods of production and use
US6433040B1 (en) * 1997-09-29 2002-08-13 Inhale Therapeutic Systems, Inc. Stabilized bioactive preparations and methods of use
US6565885B1 (en) 1997-09-29 2003-05-20 Inhale Therapeutic Systems, Inc. Methods of spray drying pharmaceutical compositions
US6946117B1 (en) * 1997-09-29 2005-09-20 Nektar Therapeutics Stabilized preparations for use in nebulizers
US20060165606A1 (en) 1997-09-29 2006-07-27 Nektar Therapeutics Pulmonary delivery particles comprising water insoluble or crystalline active agents
US6309623B1 (en) 1997-09-29 2001-10-30 Inhale Therapeutic Systems, Inc. Stabilized preparations for use in metered dose inhalers
US6252003B1 (en) 1998-06-04 2001-06-26 Kao Corporation Polymer emulsion and process for producing the same
DE19850734A1 (de) * 1998-11-04 2000-05-11 Henkel Kgaa Alkoholische kosmetische Zubereitungen
EP1150655B1 (de) * 1999-02-09 2003-09-17 Cognis Deutschland GmbH & Co. KG Verwendung von nanoskaligen chitosanen
JP2000290187A (ja) * 1999-04-05 2000-10-17 Toshio Sato キトサン入りソフトカプセル及びその製造方法
WO2000074643A1 (en) * 1999-06-04 2000-12-14 The Procter & Gamble Company Skin care sticks
US7101928B1 (en) * 1999-09-17 2006-09-05 Landec Corporation Polymeric thickeners for oil-containing compositions
DE10014529A1 (de) * 2000-03-23 2001-09-27 Cognis Deutschland Gmbh Desodorierende Zubereitungen mit nanoskaligen Chitosanen und/oder Chitosanderivaten
US7871598B1 (en) 2000-05-10 2011-01-18 Novartis Ag Stable metal ion-lipid powdered pharmaceutical compositions for drug delivery and methods of use
WO2001085136A2 (en) * 2000-05-10 2001-11-15 Alliance Pharmaceutical Corporation Phospholipid-based powders for drug delivery
US8404217B2 (en) 2000-05-10 2013-03-26 Novartis Ag Formulation for pulmonary administration of antifungal agents, and associated methods of manufacture and use
EP1443088A4 (de) * 2001-09-19 2005-01-19 Tdk Corp Künstliche fingerabdruckflüssigkeit, entsprechendes prüfverfahren für optische informationsträger sowie optischer informationsträger
EP1458360B1 (de) 2001-12-19 2011-05-11 Novartis AG Pulmonale verabreichung von aminoglykosiden
KR100566661B1 (ko) * 2003-07-16 2006-03-31 주식회사 아주의대벤쳐메딕스 땀 악취증 증상 개선효과를 가지는 조성물
JP4628671B2 (ja) * 2003-12-24 2011-02-09 乙雄 榊原 毛髪化粧料
DE102006040535A1 (de) * 2006-08-30 2008-03-13 Beiersdorf Ag Aerosolzubereitung umfassend Peloide
US7943597B2 (en) * 2008-04-08 2011-05-17 Cypress Pharmaceutical, Inc. Phosphate-binding chitosan and uses thereof
WO2013131107A1 (en) * 2012-03-02 2013-09-06 Amcol International Corporation Compositions having perspiration reduction properties
WO2014043487A2 (en) 2012-09-14 2014-03-20 The Procter & Gamble Company Aerosol antiperspirant compositions, products and methods
WO2015058935A1 (en) * 2013-10-23 2015-04-30 Unilever Plc Anti-perspirant composition
US9579265B2 (en) 2014-03-13 2017-02-28 The Procter & Gamble Company Aerosol antiperspirant compositions, products and methods
US9662285B2 (en) 2014-03-13 2017-05-30 The Procter & Gamble Company Aerosol antiperspirant compositions, products and methods
DE102014221673A1 (de) * 2014-10-24 2016-04-28 Henkel Ag & Co. Kgaa Chitosanhaltige schweißhemmende kosmetische Mittel, welche frei sind von Halogeniden und/oder Hydroxyhalogeniden von Aluminium und/oder Zirconium
WO2016103807A1 (ja) * 2014-12-24 2016-06-30 東亞合成株式会社 消臭剤及び消臭製品
US10167414B1 (en) * 2016-03-14 2019-01-01 Thomas O'Lenick Alkyl silicones as pigment coatings
WO2020093192A1 (zh) * 2018-11-05 2020-05-14 重庆小丸科贸有限公司 一种水溶性活性物颗粒及其制备方法和应用
CN112169773B (zh) * 2020-10-15 2022-09-30 重庆大学 一种增强型磁性吸附剂

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6195014A (ja) * 1984-10-15 1986-05-13 Namiko Miyata 耐塩水性のすぐれた吸水材料
JPS62190110A (ja) * 1986-02-15 1987-08-20 Fuji Boseki Kk キトサン配合化粧料
JPH0780922B2 (ja) * 1987-01-28 1995-08-30 ユニチカ株式会社 キチンスポンジ
JP2507425B2 (ja) * 1987-05-23 1996-06-12 新田ゼラチン株式会社 化粧料
JP2817968B2 (ja) * 1989-10-19 1998-10-30 根上工業株式会社 キトサン含有粒状体およびその製造方法
JPH04235906A (ja) * 1991-01-16 1992-08-25 Noevir Co Ltd メイクアップ化粧料
JP3233673B2 (ja) * 1992-03-19 2001-11-26 ジーイー東芝シリコーン株式会社 化粧料

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